Method of forming a light-emitting device with a triple junction

ABSTRACT

A light-emitting device is provided that is excellent in light emission efficiency and stability. The light-emitting device has a first part of a first dielectric constant, a second part of a second dielectric constant and a third part of a third dielectric constant, and has a triple junction where they are in contact with one another. Moreover, a first and a second electrode are provided for applying a voltage for controlling an electric field at the triple junction and in the vicinity thereof. Further, at least one of the first, the second and the third parts is a constituted by light-emitting material, and the triple junction forms a closed line.

CROSS REFERENCE TO RELATED APPLICATION

The present application is a division of U.S. application Ser. No.11/214,853, filed on Aug. 31, 2005, now U.S. Pat. No. 7,473,942 theentire disclosure of which is incorporated by reference herein.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a light-emitting device and aproduction method thereof.

2. Related Background Art

As a light-emitting device, two types of devices are known.

One is a device of current injection type, in which carrier (electronand holes) are injected into p-n junction and light is emitted byelectron-hole recombination. This type of devices of a light emittingdiode and a laser diode etc. is operated under relatively low voltages(<10V) and may be driven under DC condition.

Another is a device using electric field excitation, in which highelectric field across stacked dielectric layer and light-emitting layeris used to accelerate electrons and excite the light-emitting layer.This type of device of inorganic EL etc. is operated under relativelyhigh voltages and is driven under AC condition. A general inorganic ELhas a double insulating structure with an electrode layer, a firstinsulating layer, a light-emitting layer, a second insulating layer, anelectrode layer being stacked on a glass substrate.

These two types of device are different in their operation principles.

In this specification, the term “an electric field excitationlight-emitting device” indicates the latter type of device usingelectric field excitation.

A flat panel display (FPD) having such a light-emitting device appliedthereto has been attracting attention. As an FPD, an organicelectroluminescence display (organic EL), an inorganicelectroluminescence display (inorganic EL), a light-emitting diodedisplay (LED display) are included.

A light-emitting diode can be driven with a low voltage and is excellentin stability, but requires high temperature process for crystal growth,and is therefore difficult to be formed on a glass substrate and aplastic substrate. Therefore, as a display, its range of application islimited.

An organic EL display can be driven with a low voltage and can be formedon a glass substrate or a plastic substrate, but has a problem inreliability and durability.

With regard to inorganic display, production of a large area display iscomparatively easy, and high resistance to use environment can beexpected, but the high drive voltage is currently problematic. Recently,in Japanese Patent Application Laid-Open No. 2002-280185, a technologyon a thin film EL device with quantum size layers of alternately stackedfilms or a porous layer has been disclosed for improving light emissionefficiency.

SUMMARY OF THE INVENTION

It is, therefore, an object of the present invention to provide a novellight-emitting device which is excellent in light emission efficiency,stability and production cost.

According to a first aspect of the present invention, there is provideda light-emitting device comprising:

a first part of a first dielectric constant;

a second part of a second dielectric constant;

a third part of a third dielectric constant;

a triple junction where the first, the second and the third parts are incontact with one another; and

a first and a second electrodes,

wherein at least one of the first, the second and the third parts isconstituted by light emitting material and the triple junction forms aclosed line.

Further, the light emitting material is excited by using electric fieldbetween the first electrode and the second electrode.

According to a second aspect of the present invention, there is providedan image display apparatus using the above-mentioned light-emittingdevice.

According to a third aspect of the present invention, there is provideda method of producing an light-emitting device comprising the steps of:

1) forming a first part of a first dielectric constant; and

2) forming on the first part a thin film layer comprising a second partof a second dielectric constant and a third part of a third dielectricconstant, so as to form a triple junction with geometry of a closedline, where the three parts of the first, the second and the third partsare in contact with one another.

According to a fourth aspect of the present invention, there is provideda method of producing an light-emitting device comprising the steps of:

a) forming a member having, on a surface thereof, a first part of afirst dielectric constant and a second part of a second dielectricconstant; and

b) forming on the member a third part of a third dielectric constant, soas to form a triple junction with geometry of a closed line, where thethree parts of the first, the second and the third parts are in contactwith one another.

In the present invention, it is preferred that the triple junction hasgeometry of a closed line, especially a closed curve.

With the device and production method in accordance with the presentinvention, a light-emitting device that is excellent in emissionuniformity in a light-emitting surface (plane) and can be driven stablyat a comparatively low voltage can be realized.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a schematic sectional view showing a configuration of alight-emitting device in accordance with the present invention, and FIG.1B is an enlarged view of a portion indicated by a chain circle in FIG.1A;

FIGS. 2A and 2B are perspective views illustrating a triple junction;

FIGS. 3A, 3B, 3C, 3D, 3E, 3F, and 3G are sectional views showing aconfiguration example of a triple junction with geometry of a closedline;

FIGS. 4A, 4B and 4C are sectional views showing a magnitude relationshipof dielectric constants and an electric field around a triple junction;

FIGS. 5A, 5B and 5C are sectional views showing an example of disposinga light-emitting material;

FIG. 6A is a schematic view showing a configuration of anotherlight-emitting device in accordance with the present invention, and FIG.6B is an enlarged view of a portion indicated by a chain circle in FIG.6A;

FIGS. 7A, 7B, 7C, and 7D are schematic views showing an example of astructure of a fine-structured layer;

FIG. 8 is a schematic view showing an example of a light-emitting devicein accordance with the present invention; and

FIGS. 9A, 9B and 9C are sectional views showing a configuration of atriple junction.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

A light-emitting device in accordance with the present invention will bedescribed.

FIG. 1A is a schematic view showing a configuration of a light-emittingdevice in accordance with the present invention, and FIG. 1B is anenlarged view of a portion indicated by a chain circle in FIG. 1A.

Here, reference numeral 10 denotes a substrate; reference numeral 11denotes an electrode layer; reference numeral 12 denotes a firstinsulating layer; reference numeral 13 denotes a first fine-structuredlayer; reference numeral 14 denotes a light-emitting layer; referencenumeral 15 denotes a second fine-structured layer; reference numeral 16denotes a second insulating layer; reference numeral 17 denotes atransparent electrode layer (second electrode layer); reference numeral18 denotes a power supply; and reference numeral 19 denotes light.

As shown by the enlarged view of FIG. 1B, the fine-structured layer,which has a second part 102 of a second dielectric constant and a thirdpart 103 of a third dielectric constant, is in contact with a first part101 (light-emitting layer 14) of a first dielectric constant. That is,the second part 102 and the third part 103 are in contact with the firstpart 101 to form a triple junction 100.

The triple junction will be described. As shown in FIGS. 2A and 2B, thetriple junction is a junction where a first part 101 of a firstdielectric constant ∈1, the second part 102 of a second dielectricconstant ∈2 and the third part 103 of a third dielectric constant ∈3 aremutually in contact with one another.

As the geometry of the triple junction, there are included geometrywhere the three materials are in contact with one another at a point andgeometry where the three materials are in contact with one another in aline as shown in FIG. 2A.

In the present invention, the triple junction with geometry of a closedline is preferable. The triple junction with geometry of a closed lineused in the present invention may have vertexes as in a polygon, or maybe curved as shown in FIG. 2B (without vertex). Alternatively, thetriple junction with geometry of a closed line may be a closed lineconsisting of a curve and a straight line. In the figure, referencenumeral 100 b denotes a triple junction with geometry of a closed curve.In the light-emitting device in accordance with the present invent,provision of only a single triple junction may be included. Also,provision of a plurality of triple junctions is more preferable. Aclosed curve makes it possible to dispose the triple junction in highdensity, thereby providing a device with a higher light emission.Further, the configuration having a plurality of closed curves is morepreferable from the point of view of higher density of the triplejunction.

In the light-emitting device in accordance with the present invention,because excitation and light emission mainly take place in a triplejunction and in the vicinity thereof, it is preferred that the triplejunctions are provided densely. By providing the triple junctionsdensely, improvement of luminance accompanied with increase inlight-emitting sites, and improvement of uniformity of in-planeluminance distribution can be accomplished.

Moreover, from the point of view of providing the triple junctionsdensely, it is preferable that the second part 102 of the seconddielectric constant in FIG. 2B is small, and for example, that thelength of the closed line of triple junction is not more than 1 μm.

In addition, in order to intensify an electric field strength locally atthe triple junction, it is preferred that the spacing between adjacenttriple junctions is large to a certain extent, and, for example, thatthe spacing is 10 nm or more.

The transparent electrode layer 17 and the electrode layer 11 areelectrically connected to the power supply 18 for driving. The powersupply may be a pulse power supply, an AC power supply and the like.

Thus, the light-emitting device in accordance with the present inventionhas a first part of a first dielectric constant, a second part of asecond dielectric constant and a third part of a third dielectricconstant, and has a triple junction where they are in contact with oneanother. Moreover, the device has a first and a second electrodes forapplying a voltage for controlling an electric field at the triplejunction and in the vicinity thereof. Further, at least one of thefirst, the second and the third parts is a light emitting material andthe triple junction forms a closed line.

When applying a voltage from the power supply 18 to the electrodes 11,17, an electric field is generated between the electrodes, and arelatively larger electric field strength may be generated at the triplejunction and in the vicinity thereof locally. That is, electronsinjected from, for example, an interface state between the cathode side(low potential side) insulating layer and the fine-structured layer areefficiently accelerated-via the triple junction to generate hotelectrons having a high energy. The sufficiently energized hot electronswill excite the light-emitting material (layer) efficiently, so thatgood light emission can be implemented. The electrons injected into thelight-emitting layer are trapped by, for example, an interface statebetween the anode side insulating layer and the fine-structured layer.Successively, when an external pulse voltage in an opposite polarity isapplied, the anode and the cathode are reversed, so that the sameexcitation and light emission process is repeated in the oppositedirection.

Thus, in the electric field excitation light-emitting device inaccordance with the present invention, efficient excitation is achievedby means of a local high electric field generated at the triple junctionand in the vicinity thereof. Thereby, this gives rise to efficient lightemission.

In addition, in the present invention, because many triple junctions(light-emitting sites) are densely dispersed in the device, thelight-emitting layer can be excited uniformly throughout the plane.

In addition, because a number of local light-emitting sites (triplejunctions) are uniformly dispersed in the plane, damage to the deviceresulting from energy loss due to concentration to one portion of thedevice hardly takes place. This can provide a light-emitting device thatis excellent in reliability and stability.

In general, for operating an electric field excitation light-emittingdevice it is necessary to give rise to an electric field strength of acertain threshold value or more. However, in the present invention, arelatively low external voltage makes it possible to generate a localelectric field strength of the threshold value or more at the triplejunction. At this time, the electric field strength at a portion apartfrom the triple junction is lower than the triple junction. Such aconfiguration enables light emission with a low voltage, and moreoverlow voltage operation enables to improve durability of the deviceagainst an excess voltage.

FIGS. 3A, 3B, 3C, 3D, 3E, 3F, and 3G are views showing a configurationexample of triple junctions. The figures are sectional views and eachtriple junction has geometry of a line in the direction perpendicular tothe drawing plane. As with FIG. 1A, it is presumed that an externalvoltage is applied in the upward and downward direction in the figureswith electrodes (not shown). In the figures, the direction of externalvoltage application is indicated by an arrow.

FIG. 3A shows a configuration having the least limit to the triplejunction. A first part 101 of a first dielectric constant ∈1, a secondpart 102 of a second dielectric constant ∈2 and a third part 103 of athird dielectric constant ∈3 are in contact one another.

FIG. 3B is an example in which an interface between a first part and asecond part and an interface between a second part and a third part andan interface between a first part and a third part are each configuredas a substantially straight line in the sectional view.

FIG. 3C is a case where a interface between a first part and a secondpart and an interface between the first part and a third part areconnected to form a straight line continuously, and moreover thestraight line is perpendicular to the direction of the voltageapplication. Such a configuration can be produced by stacking afine-structured layer consisting of a second part and a third part and alayer of a first dielectric constant, and therefore can be said to becomparatively readily producible. In addition, even if the differencebetween the second dielectric constant and the third dielectric constantis small, a comparatively large local electric field arises in thevicinity of the triple junction, which is therefore preferable.

FIG. 3D is a case where an interface between a second part and a thirdpart is parallel to the direction of voltage application. Even if thedifference between the second dielectric constant and the thirddielectric constant is comparatively small, such a configuration givesrise to a comparatively large local electric field in the vicinity ofthe triple junction, which is therefore preferable.

The configuration shown in FIG. 3E having the characteristics of FIGS.3C and 3D in combination is more preferable. As another example, theconfiguration shown in FIG. 3F may be included. In addition, theforegoing description has been made taking as an example a triplejunction where three materials are in contact with one another. Also, ajunction where more than three (e.g., four) parts are in contact withone another is shown in FIG. 3G. This junction can be expected toexhibit those effects which are equivalent to or better than theabove-mentioned effects.

Taking the configuration shown in FIG. 3E as an example, electric fieldstrengths in the vicinity of the triple junction are shown in FIGS. 4A,4B and 4C. FIGS. 4A, 4B and 4C are different from each other inmagnitude relationship between dielectric constants ∈1, ∈2 and ∈3. Inthe figures, the size and direction of an arrow indicate the relativestrength and direction of an electric field.

In every case, as shown in FIGS. 4A, 4B and 4C, the electric fieldstrength at the triple junction and in the vicinity thereof is largerthan at the peripheral parts. In particular, the case of FIG. 4B ischaracterized in that the local electric field strength in the vicinityof the triple junction is intensified compared with the cases of FIGS.4A and 4C. Moreover, it is further characterized in that the portion ofthis intensified electric field strength is narrow (highly localized)and the microscopic direction of the electric field vector is inclinedwith respect to the direction of voltage application (macroscopicelectric field direction). This configuration shown in FIG. 4B canattain a locally intensified electric field strength with a smallexternal voltage, and therefore is one of preferable examples from thepoint of view of reducing the drive voltage.

There is no particular limitation to the values of dielectric constants∈1, ∈2 and ∈3, and any value between 1 to several 1000 is available, butwhen the relative ratio is large, the local electric field strength inthe vicinity of the triple junction can be intensified, which istherefore preferable.

In addition, as to the first material, the second material and the thirdmaterial disposed around the above described triple junction, there isno particular limitation as long as it is a dielectric material. Fromthe point of view of stable dielectric property and effective electronacceleration (at the time of light emission), oxides are preferable. Forexample, SiO₂, Al₂O₃, TiO₂, Y₂O₃, Ta₂O₅, HfO₂, ZrO₂, La₂O₃, MgO, BaTiO₃and the like are included. In order to control the dielectric constant,composite oxides thereof may also be employed.

In the present invention, at least one of the first, the second and thethird parts may be comprised of a light-emitting material. Thereby,electrons accelerated with the electric field in the vicinity of thetriple junction can excite the light-emitting material effectively.

For example, as shown in FIG. 5A, a configuration is included in which alayer of a light-emitting material (a first part of a first dielectricconstant ∈1) and a fine-structured layer consisting of a second part ofa second dielectric constant ∈2 and a third part of a third dielectricconstant ∈3 are stacked on each other. The example shown in FIGS. 1A and1B also has the same configuration as above.

Otherwise, as shown in FIG. 5B, a configuration is also included inwhich a layer of a first dielectric constant ∈1 and a fine-structuredlayer consisting of a light-emitting part (a second part of a seconddielectric constant ∈2) and a third part of a third dielectric constant∈3 are stacked on each other. FIG. 5C is an example in which the thirdpart of the third dielectric constant in FIG. 5B is also constituted asa light-emitting part. Further, all of the first, the second and thethird parts can be constituted of light-emitting material. When therespective parts constituted by light-emitting material are designed toprovide different emission colors, multi-color mixing or awhite-light-emitting device can be attained.

In addition, in order to excite alight-emitting material effectivelywith electrons accelerated by an intense electric field in the vicinityof a triple junction, it is preferable to dispose the light-emittingmaterial at a starting point of the arrow (thick arrow) indicating anintensified electric field in FIGS. 4A, 4B and 4C. That is, taking thecase of FIG. 4B referred to as a preferable example above, thearrangement of FIG. 5A is preferable in which the first part ofdielectric constant ∈1 is a light-emitting material. On the other hand,in the case where the direction of voltage application is reversed, thedirection of electric field (the direction of the arrow) is reversed,and therefore an arrangement of disposing a light-emitting material atthe final point of the arrow is also preferable. That is, in the case ofFIG. 4B which was taken as a preferable example above, the dispositionshown in FIG. 5B in which the second part of dielectric constant ∈2 is alight-emitting material.

As the light-emitting material, there are included light-emittingmaterials having an emission center, such as ZnS:Mn, SrS:(Ce,Eu),CaS:Eu, ZnS:(Tb, F), CaS:Ce, SrS:Ce, CaGa₂S₄:Ce, BaAl₂S₄:Eu, Ga₂O₃:Eu,Y₂O₃:Eu, Zn₂SiO₄:Mn, ZnGa₂O₄:Mn, Y₂O₂S:Eu³⁺, Gd₂O₂S:Eu³⁺, YVO₄:Eu³⁺,Y₂O₂S:(Eu,Sm), SrTiO₃:Pr, BaSi₂Al₂O₈:Eu²⁺, BaMg₂Al₁₆O₂₇:Eu²⁺ andY_(0.65)Gd_(0.35)BO₃:Eu³⁺, La₂O₂S:Eu³⁺, Ba₂SiO₄:Eu²⁺, Zn(Ga,Al)₂O₄:Mn,Y₃(Al,Ga)₅O₁₂:Tb, Y₂SiO₅:Tb, ZnS:Cu, Zn₂SiO₄:Mn, BaAl₂Si₂O₈:Eu²⁺,BaMgAl₁₄O₂₃:Eu²⁺, Y₂SiO₅:Ce, and ZnGa₂O₄:Eu.

In addition to the above mentioned, there may also be used tungstenoxides such as ZnWO₄, MgWO₄ and the like; molybdenum oxides such asZnMoO₄, SrMO₄ and the like; vanadium oxides such as YVO₄ and the like;and europium oxides such as Eu₂SiO₄, EuSiO and the like; organiclight-emitting materials including Alq₃ and Ir(ppy); semiconductormaterials including ZnSe, CdSe, ZnTe, GaP, GaN, and ZnO; and fineparticles thereof.

Further, FIGS. 1A and 1B are conceptual diagrams of a device of a typein which a light is taken out from a side opposite to the substrate sideof the device. On the other hand, by forming the electrode layer 11 of atransparent electrode, a device of a type in which a light is taken outfrom the substrate side of the device is also available. In addition,FIGS. 1A and 1B feature a device of a double insulation type having thefirst and the second insulating layers, and these insulating layers canenhance the insulating characteristics of the device and can improvereliability of the device. Also the insulating layers can be omitted inthe case where only the light-emitting layer and the fine-structuredlayer can provide sufficient insulating characteristics. Alternatively,either one of the insulating layers may be provided.

Further, in the configuration shown in FIGS. 1A and 1B, the first andthe second fine-structured layers are provided and the triple junctionsare formed on the interfaces of the respective layers with thelight-emitting layer. Also, the configuration only either one of thefine-structured layers may be provide.

Moreover, FIGS. 1A and 1B feature the two fine-structured layers and thesingle light-emitting layer. Also, as shown in FIG. 8, a plurality offine-structured layers and a plurality of light-emitting layers may bestacked on each other alternately.

The respective layers of the configuration shown in FIGS. 1A and 1B 1will be described.

At first, the fine-structured layers 13 and 15 will be described.

FIGS. 7A, 7B, 7C, and 7D are schematic views each showing an example ofa structure of a fine-structured layer 13. The fine-structured layer 13has, inside the layer plane, a first part 21 consisting of a firstmaterial and a second part 22 consisting of a second material. Inparticular, it is characterized by having a fine structure of a size inthe order of submicron to nanometer. In FIGS. 1A and 1B, for convenienceof presentation, the first parts and the second parts are depicted in alarge size, but their actual sizes are very small compared with the sizeof the device.

Respectively in FIGS. 7A to 7D, a plan view (upper one) and a sectionalview (lower one) are depicted. FIG. 7A is an example of a structurehaving regions of the first material and the second material; FIG. 7B isan example of a structure having a cylindrical material buried in amatrix; FIG. 7C is an example of a lamellar structure; and FIG. 7D is anexample of a structure having regions of the first material 21, thesecond material 22 and third material 23.

As shown in FIGS. 7A to 7D, the fine-structured layer has plural partsconsisting of different materials (the first part 21 consisting of thefirst material and the second part 22 consisting of the secondmaterial). The fine-structured layer is stacked onto the layer 23consisting of still another third material to form a triple junctionwith geometry of a closed line. The sizes of the respective parts are inthe order of several nanometers to several micrometers.

The structure in FIG. 7B has columnar parts (first-material part 21) isburied in a matrix (second material part 22). Otherwise, a lamellarstructure such as shown in FIG. 7C is included. These structures can beproduced in self-organizing techniques utilizing a eutectic reaction,and therefore can be described as a preferable structure from the pointof view of low-cost production. In FIG. 7D, an example having threeparts of different materials is depicted.

The thickness of the fine-structured layer is within the range ofseveral nanometers to several 100 nanometers. As to the material forconstituting the fine-structured layer, there is no limitation as longas it is a dielectric material. From the point of view of ensuringstable dielectric property at the time of application of a high electricfield and effective electron acceleration (at the time of lightemission), it is preferable to use an oxide. For example, SiO₂, Al₂O₃,TiO₂, Y₂O₃, Ta₂O₅, HfO₂, ZrO₂, La₂O₃, MgO, BaTiO₃ and the like areincluded. In order to control the dielectric constant, a composite oxidethereof may also be used.

Reduction in size of the first and second parts in the fine-structuredlayer leads to increase in density of the triple junctions andconsequently leads to increase in light-emitting sites. Moreover, thisis more preferable from the point of view of in-plane uniformity oflight emission characteristics.

In addition, it is preferred that the first and the second parts arearranged to form periodical structures. That is, a configuration inwhich first parts are arranged regularly in a second part is a morepreferable configuration. This structure enables the device within-plane uniformity of light emission characteristics, where similarlight-emitting sites are densely arranged.

In the case of taking out a light from the substrate side, it ispreferable that the substrate 10 is made of transparent glass or plasticsuch that the emitted light transmits therethrough. In the case oftaking out a light from the top of the device as shown in FIG. 1A, thetype of the substrate is not limited. In this case, as the substrate,glass, plastic, ceramic and semiconductor substrate etc. are utilizable.

It is preferable that the transparent electrode layer 17 has bothfeatures of conductivity for functioning as an electrode andtransparency that allows the emitted light to transmit therethrough.Examples thereof include a transparent conductive film such as dopedIn₂O₃, SnO₂, ZnO, ITO, or the like.

As the electrode layer 11, respective kinds of metals, alloys andtransparent conductive films such as Al, Au, Pt, Ag, Ta, Ni and the likecan be utilized. As the first and the second insulating layers 12 and16, there may be included dielectric such as SiO₂, Si₃N₄, Al₂O₃, TiO₂,Y₂O₃, Ta₂O₅, BaTiO₃ and the like. The film thickness of the insulatinglayers is generally within the range of several 100 to severalmicrometers.

The light-emitting layer 14 is a layer that emits light under operation.The thickness of the light-emitting layer is preferably within the rangeof 50 nm to 1 μm. As for the material constituting the light-emittinglayer, the above described light-emitting materials can be used.

For film formation of the fine-structured layer, light-emitting layer,transparent conductive layer and electrode layer, there may be used anythin film formation method including a gas phase method such as vacuumevaporation, sputtering, electron beam evaporation, etc., a liquid phasemethod such as plating, etc. and a solid-phase method such as sol-gelprocess, etc.

In particular, for producing the above described fine-structured layer,a eutectic reaction may be preferably used. Especially the sputteringmethod that can supply high energy particles to a substrate ispreferable method to use eutectic reaction.

FIGS. 9A, 9B and 9C show a method of providing a triple junction in aconfiguration different from the example shown in FIG. 1 in which thefine-structured layer is provided.

First, as shown in FIG. 9A, a configuration is included in which asecond part 102 consisting of a second dielectric material with a fineparticle shape is embedded in a layer structure of a first part 101consisting of a first dielectric material and a second part 103consisting of a third dielectric material to form a triple junction 100.

Secondly, as shown in FIG. 9B, a second part 102 consisting of anisland-shaped film is formed on a layer (substrate) 101 as a first part,and thereon a layer (a third part) 103 is further over-coated to form atriple junction (point) 100.

Thirdly, as shown in FIG. 9C, a configuration is included in which apart of the surface of a fine particle 101 (as a first part) is coveredwith a second part 102, and thereafter the fine particles are dispersedin a film 103 as a third part to form a triple junction (point) 100.

With such methods, a plurality of triple junctions with geometry ofclosed curve may be formed.

EXAMPLES

The present invention will be further described by way of examples asfollows. However, the present invention will not be limited to thefollowing examples but includes those included in the above describedconcepts.

Example 1

A light-emitting device of the present example has a configurationsimilar to the configuration shown in FIGS. 1A and 1B.

FIG. 1A is a schematic view showing a configuration of a light-emittingdevice in accordance with the present invention, and FIG. 1B is anenlarged view of a portion indicated by a chain circle in FIG. 1A.

In the figures, reference numeral 10 denotes a substrate; referencenumeral 11 denotes an electrode layer; reference numeral 12 denotes afirst insulating layer; reference numeral 13 denotes a firstfine-structured layer; reference numeral 14 denotes a light emittinglayer; reference numeral 15 denotes a second fine-structured layer;reference numeral 16 denotes a second insulating layer; referencenumeral 17 denotes a transparent electrode layer (second electrodelayer); reference numeral 18 denotes a power supply; and referencenumeral 19 denotes light. However, the present example is configuredwith the first insulating layer 12 and the second fine-structured layer15 being omitted.

As shown in FIG. 7B, the fine-structured layer of the present examplehas, inside the layer plane, a first part 21 consisting of a firstmaterial and a second part 22 consisting of a second material. The firstpart 21 and the second part 22 in FIG. 7B respectively correspond to thesecond part 102 and the third part 103 in FIGS. 1A and 1B. Further, thefirst material contains alumina (dielectric constant: ˜8) as a maincomponent, while the second material contains silicon oxide (dielectricconstant: ˜4) as a main component. A number of triple junctions withgeometry of a closed line will be disposed at an interface between thefine-structured layer and the light-emitting layer (the first part ofthe first dielectric constant). Incidentally, the light-emitting layerconsists of ZnS:Mn (dielectric constant: ˜10).

In this example, the triple junction is configured as in FIG. 3E, themagnitude relationship between dielectric constants of the respectiveparts 101, 102 and 103 is set as in FIG. 4C (∈1>∈2>∈3) and thearrangement of the light-emitting material is configured as in FIG. 5A(the material of ∈1 being the light-emitting material).

Description will be made along the production steps.

As the substrate 10, a quartz substrate was used. On the substrate 10,Ta in a thickness of 100 nm was deposited as the electrode layer 11 by amagnetron sputtering method.

Next, the fine-structured layer 13 was formed. The fine-structured layerwas produced by firstly forming a structural member made of Al and Si bya magnetron sputtering method and then anodizing the structural member.The structural member made of Al and Si was configured by a cylindricalpart containing Al as a main component and a matrix part containing Sias a main component and surrounding the cylindrical part, as shown inFIG. 7B. By anodizing the structural member, a fine-structured layerconsisting of a cylindrical part containing alumina as a main componentand a matrix part containing silicon oxide as a main component andsurrounding the cylindrical part could be prepared.

The structural member made of Al and Si was formed by a magnetronsputtering method by use of a target consisting of a mixture of Al andSi. At this time, in order to uniformly disperse the columnar partsconsisting of Al in the Si matrix, it is preferable to set the target soas to face the substrate. Changing the composition ratio of Al to Simakes it possible to control the percentages of the parts of Al and Si.For example, the Al cylinder has a diameter of 1 to 20 nm and thespacing therebetween is 5 to 30 nm.

In the present example, the film with the composition ratio of Al to Sibeing set to 56:44 was deposited at room temperature and a sputteringpower of 120 W. The size of the aluminum part was approximately 8 nm andthe spacing was about 12 nm. And the structural member had theconfiguration that the cylindrical aluminum was buried in the matrixconsisting of silicon, as shown in FIG. 2B. The film thickness was about70 nm.

Subsequently, the structural member made of Al and Si was anodized in a0.1 M aqueous ammonium tartrate solution at a voltage of about 50 V,where anode of the substrate with the structural member was arranged soas to face a platinum electrode (cathode). The aluminum and silicon ofthe structural member was oxidized under the anodizing process. Thus, anoxide structural member consisting of the alumina part (first material)and the silicon oxide part (second material) such as shown in FIG. 7Bwas formed.

The fine-structured layer had a thickness of approximately 80 nm and wasconfigured by disposing the alumina parts with a diameter ofapproximately 8 nm dispersedly in the matrix of silicon oxide. Thesilicon oxide part may partly comprise a silicon part not subjected tooxidation.

Next, as the light emitting layer 14, film formation was implemented byan electron beam evaporation method at a substrate temperature 200° C.to deposit ZnS:Mn in a thickness of 500 nm.

Moreover, tantalum oxide was deposited thereon in a thickness of 300 nmas the second insulating layer 16 and then ITO was deposited thereon ina thickness of 200 nm as the transparent electrode layer 17.

The transparent electrode layer and the electrode layer wererespectively connected electrically to a power supply for driving. Thedriving power supply used was a pulse voltage supply. When applyingpositive and negative rectangular voltages alternately and increasingthe voltage gradually, light emission was attained at about 180 V ormore. At this time, the pulse width was 1 ms and the pulse repetitionfrequency was 50 Hz.

In the electric field excitation light-emitting device of the presentexample, by providing a fine-structured layer, a configuration havingtriple junctions with geometry of a closed line disposed densely isprovided. By accelerating electrons with a locally intensified electricfield in the vicinity of the triple junctions, effective excitation of alight-emitting material is attained. This enables uniform light emissionin the device plane, and the stability thereof is good.

Example 2

A light-emitting device of the present example has a configurationsimilar to the configuration shown in FIGS. 1A and 1B.

As shown in FIG. 7B, the fine-structured layer of the present examplehas, inside the layer plane, a first part 21 consisting of a firstmaterial and a second part 22 consisting of a second material. The firstpart 21 and the second part 22 in FIG. 7B respectively correspond to thesecond part 102 and the third part 103 in FIGS. 1A and 1B. Further, thefirst material contains iron oxide (dielectric constant: about 12 to 16)as a main component, while the second material contains silicon oxide(dielectric constant: ˜4) as a main component. A number of triplejunctions with geometry of a closed line will be disposed at aninterface between the fine-structured layer and the light-emitting layer(the first part of the first dielectric constant). Incidentally, thelight-emitting layer is made of Y₂O₃:Eu (dielectric constant: ˜12).

In this example, the triple junction is configured as in FIG. 3E, themagnitude relationship between dielectric constants of the respectiveparts 101, 102 and 103 is set as in FIG. 4B (∈2>∈1>∈3) and thearrangement of the light-emitting material is configured as in FIG. 5A(the material of ∈1 being the light-emitting material).

Description will be made along the production steps.

As the substrate 10, a quartz substrate was used. On the substrate 10,Pt film in a thickness of 200 nm was deposited as the electrode layer 11by a magnetron sputtering method. A Ti film in a thickness of 10 nm waspre-deposited as a base layer.

Subsequently, a tantalum oxide thin film of 300 nm in thickness wasformed as the first insulating layer 12. Next, the fine-structured layer13 was formed. The fine-structured layer was made by firstly forming afilm made of Fe, Si and O with a magnetron sputtering method andpost-heat-treatment at 600° C. in the atmosphere. In the sputtering, amixture of FeO powder and SiO₂ powder in a volumetric percentage ofabout 30% was used as a target. Thereby, as shown in FIG. 7B, afine-structured layer consisting of a cylindrical part containing ironoxide as a main component and a matrix part containing silicon oxide asa main component and surrounding the cylindrical part could be prepared.

In the present example, the size of the iron oxide part wasapproximately 4 nm, the fine-structured layer had the configuration suchthat the cylindrical member was buried in the matrix consisting ofsilicon oxide as shown in FIG. 2B, and the film thickness was about 50nm.

Next, as the light emitting layer 14, film formation was implemented bya sputtering method to deposit Y₂O₃:Eu in a thickness of 400 nm, whichwas subsequently subjected to heat treatment of 700° C.

Further, the second fine-structured layer 15 was formed by following thesame procedure as the first fine-structured layer 13.

Moreover, a thin film of tantalum oxide was formed thereon in athickness of 300 nm as the second insulating layer 16 and then ITO wasdeposited thereon in a thickness of 200 nm as the transparent electrodelayer 17.

The transparent electrode layer and the electrode layer wererespectively connected electrically to a power supply for driving. Thedriving power supply used was a pulse voltage supply. When applyingpositive and negative rectangular voltages alternately and increasingthe voltage gradually, light emission was attained at about 170 V ormore. At this time, the pulse width was 1 ms and the pulse repetitionfrequency was 50 Hz.

In the electric field excitation light-emitting device of the presentexample, by providing a fine-structured layer, a configuration havingtriple junctions with geometry of a closed line disposed densely isprovided. By accelerating electrons with a locally intensified electricfield in the vicinity of the triple junctions, effective excitation of alight-emitting material is attained. This enables uniform light emissioninside the device plane, and the stability thereof is good. This attainsuniform light emission inside the device plane, and stability thereof isgood. Further, by providing the first and the second insulating layers,the device has a high resistance to an excess voltage.

Example 3

A light-emitting device of the present example has a configurationsimilar to the configuration shown in FIGS. 1A and 1B.

However, the present example is configured with the first insulatinglayer 12 and the second insulating layer 16 being omitted, since thefine-structured layers have a sufficient insulating property.

In addition, the electrode layer 11 is formed of a transparentelectrode, and the present example is a light-emitting device of a typein which a light is taken out from the rear side of the substrate.

As shown in FIG. 7C, the fine-structured layer of the present examplehas, inside the layer plane, a first part 21 consisting of a firstmaterial and a second part 22 consisting of a second material. The firstpart 21 and the second part 22 in FIG. 7C respectively correspond to thesecond part 102 and the third part 103 in FIGS. 1A and 1B. Further, thefirst material contains zirconia (dielectric constant: about 20 to 25)as a main component, while the second material contains alumina(dielectric constant: ˜8) as a main component. A number of triplejunctions with geometry of a closed line will be disposed at aninterface between the fine-structured layer and the light-emitting layer(the first part of the first dielectric constant). Incidentally, thelight-emitting layer is made of ZnWO₄ (dielectric constant: 10 to 15).

In this example, the triple junction is configured as in FIG. 3E, themagnitude relationship between dielectric constants of the respectiveparts 101, 102 and 103 is set as in FIG. 4B (∈2>∈1>∈3) and thearrangement of the light-emitting material is configured as in FIG. 5A(the material of ∈1 being the light-emitting material).

As the substrate, a YSZ single-crystal substrate (111) was used. On thesubstrate, film formation was implemented to deposit ITO in a thicknessof 300 nm as the transparent electrode layer 11 with a magnetronsputtering method. The substrate temperature was set to 700° C.

Next, as the first fine-structured layer 13, film formation wasimplemented to deposit an oxide structural member of Zr and Al in athickness of 250 nm. A ZrO₂ (including 8 mol % of Y₂O₃) target and anAl₂O₃ target were prepared and binary simultaneous film formation waseffected with a magnetron sputtering method. The substrate temperaturewas set to approximately 800° C. and the atmosphere used was a mixtureof Ar and O₂. The gas pressure was 0.5 Pa and the flow rate ratio of Arto O₂ was 5:2. The power inputs to the respective targets were adjustedsuch that the composition ratio of Zr to Al in the formed film wasapproximately 1:4. In this thin film, the region containing ZrO₂ as amain component and the region containing Al₂O as a main component werearranged lamellarly as shown in FIG. 2C. The width of the ZrO₂ regionwas approximately 50 nm.

Next, as the light emitting layer 14, film formation was implemented toform a thin film containing ZnWO₄ as a main component in a thickness of400 nm. A ZnWO₄ target was prepared and film formation was effected witha magnetron sputtering method. The substrate temperature at the time ofthe film formation was approximately 800° C. and the atmosphere used wasa mixture of Ar and O₂. The gas pressure was 0.5 Pa and the flow rateratio of Ar to O₂ was 5:2.

Next, the second fine-structured layer 15 was formed by following thesame procedure as the first fine-structured layer 13.

Then, as the electrode layer 17, film formation was implemented with avacuum evaporation to deposit Al in a thickness of 200 nm, therebycompleting a light-emitting device.

The transparent electrode layer and the electrode layer wererespectively connected electrically to a power supply for driving. Thedriving power supply used was a pulse voltage supply. When applyingpositive and negative rectangular voltages alternately and increasingthe voltage gradually, light emission was attained at about 160 V ormore. At this time, the pulse width was 1 ms and the pulse repetitionfrequency was 50 Hz.

In the electric field excitation light-emitting device of the presentexample, by providing the fine-structured layers excellent in insulatingproperty, the first and the second insulating layers can be omitted.Further, by adopting the configuration having the triple junctionsincluding triple junctions with geometry of a closed line densely, it ispossible to attain uniform light emission inside the device plane, andthe stability thereof is good.

Example 4

A light-emitting device of the present example is an example withfine-structured layers and light-emitting layers being stacked on eachother alternately, as shown in FIG. 8.

After forming a transparent electrode layer 17 on a YSZ single-crystalsubstrate 10 by following the same procedure as in Example 3, a filmmade of tantalum oxide with a thickness of 150 nm was formed as a firstinsulating layer 12.

Subsequently, light emitting layers 14 and fine-structured layers 13were alternately stacked on each other. The formation procedure of thelight-emitting layers and the fine-structured layers was the same as inExample 3. The thicknesses of the light emitting layer and thefine-structured layer were respectively 50 nm and 20 nm, and the numbersof the light emitting layers and the fine-structured layers asalternately stacked were each 7.

Subsequently, a film made of tantalum oxide with a thickness of 150 nmwas formed as a second insulating layer 16, and moreover as an electrodelayer 11, film formation was implemented with vacuum evaporation todeposit Al in a thickness of 200 nm, thereby completing a light-emittingdevice.

The transparent electrode layer 17 and the electrode layer 11 wererespectively connected electrically to a power supply 18 for driving.The driving power supply 18 used was a pulse voltage supply. Whenapplying positive and negative rectangular voltages alternately andincreasing the voltage gradually, light emission was attained at about190 V or more. At this time, the pulse width was 1 ms and the pulserepetition frequency was 50 Hz.

The electric field excitation light-emitting device of the presentexample is an example in which the fine-structured layers and thelight-emitting layers are stacked to thereby dispose the triplejunctions densely. This enables uniform light emission inside the deviceplane, and the stability thereof is good.

Example 5

A light-emitting device of the present example has a configuration shownin FIGS. 6A and 6B, in which a light emitting layer 81 having a finestructure is provided between a first insulating layer 12 and a secondinsulating layer 16 and triple junctions are disposed between theinsulating layers and the light emitting layer.

As shown in FIG. 7B, the light-emitting layer 81 having the finestructure of the present example has, inside the layer plane, parts 21consisting of a first material and parts 22 consisting of a secondmaterial. The first part 21 and the second part 22 in FIG. 7Brespectively correspond to the second part 102 and the third part 103 inFIG. 6B.

Further, the first material is a composite oxide of Zn and W (estimateddielectric constant: ˜15) and contains ZnWO₄ as a main component, whilethe second material contains zinc oxide (dielectric constant: ˜8) as amain component. The first material and the second material are each alight-emitting material. A number of triple junctions with geometry of aclosed line will be disposed on interfaces between the light emittinglayer having the fine structure and the insulating layers. Moreover, thefirst insulating layer contains alumina (dielectric constant: ˜8) as amain component while the second insulating layer is a composite oxide ofBa and Ti (dielectric constant: ˜300). In this example, the triplejunction with geometry of a closed line is configured as in FIG. 3E andthe arrangement of the light-emitting material is configured as in FIG.5C.

In this example, the triple junction is configured as in FIG. 3E and thearrangement of the light-emitting material is configured as in FIG. 5C(the materials of ∈2 and ∈3 being light-emitting materials.

As for the magnitude relationship of dielectric constants, the triplejunction formed by the first insulating layer and the light-emittinglayer 81 having a fine structure is configured as in FIG. 4A (∈2>∈3>∈1)or as in FIG. 4B (∈2>∈1>∈3). The triple junction with geometry of aclosed line formed by the second insulating layer and the light-emittinglayer 81 having a fine structure is configured as in FIG. 4C (∈1>∈2>∈3).

As the substrate 10, a quartz substrate was used. On the substrate 10,film formation was implemented to deposit Pt in a thickness of 200 nm asthe electrode layer 11 with a magnetron sputtering method. As a baselayer, a Ti film was deposited in a thickness of 10 nm.

Subsequently, a thin film of alumina was formed in a thickness of 100 nmas the first insulating layer 12.

Next, as the layer 81 having a fine structure, film formation wasimplemented to deposit an oxide structural member of Zn and W in athickness of 500 nm. A ZnO target and a WO₃ target were prepared andbinary simultaneous film formation was effected with a magnetronsputtering method. The substrate temperature was set to approximately800° C. and the atmosphere employed was a mixture of Ar and O₂. The gaspressure was 0.5 Pa and the flow rate ratio of Ar to O₂ was 5.2. Thepower inputs to the respective targets were adjusted such that thecomposition ratio of Zn to W in the formed film was approximately 2:1.In this thin film, the region containing ZnO as a main component and theregion containing ZnWO₄ as a main component were arranged as shown inFIG. 7B. The size of the ZnWO₄ region was approximately 60 nm.

Next, the second insulating layer 16 was formed. A BaTiO₃ target wasprepared and a layer of a composite oxide of Ba and Ti was formed in athickness of 500 nm with a magnetron sputtering method.

Next, as the electrode layer 17, a film of ITO with a thickness of 200nm was formed, thereby completing a light-emitting device.

The transparent electrode layer and the electrode layer wererespectively connected electrically to a power supply 18 for drive. Thedriving power supply employed was a pulse voltage supply. When applyingpositive and negative rectangular voltages alternately and increasingthe voltage gradually, light emission was attained at about 140 V ormore. At this time, the pulse width was 1 ms and the pulse repetitionfrequency was 50 Hz.

The present example is a mixed color light-emitting device that providesa mixture of light emission in the vicinity of the wavelength 500 nm ofZnWO₄ and light emission of the wavelength of about 600 nm due to animpurity level of ZnO.

The electric field excitation light-emitting device of the presentexample has a configuration in which the fine-structured layer of anano-size is provided to thereby dispose the triple junctions densely.This enables uniform light emission inside the device plane, and thestability thereof is good.

Next, examples of applying the light-emitting device of the presentinvention to an image display apparatus, a lighting equipment and aprinter will be described.

The light-emitting device of Example 1 can be used as an image displayapparatus by arranging and wiring these device in a matrix pattern fordriving. A color image can be obtained by creating colors through RGBfilters using white-light emitting devices. Also, a color image displaywas constituted by arranging Red, Green and Blue light-emitting device.In addition, with a blue-light emitting device, green and red colors canbe obtained by color conversion using a fluorescent material.

Further, in the case where the light-emitting device of the presentinvention is used in a lighting equipment, there may be used a method ofusing a white-light emitting device, a method of stacking layers ofRGB-light emitting device in the vertical direction and a method ofemitting blue or ultraviolet light and then converting the light intolight of RGB.

Moreover, the light-emitting device of the present invention can be usedfor a printer such as a letter printing apparatus by arranging thelight-emitting devices in a line and driving them, instead of scanning alaser beam with a polygon mirror.

With the device and production method of the present invention, alight-emitting device can be realized that is excellent in emissionuniformity in a light-emitting surface and can be driven stably at acomparatively low voltage. The light-emitting device of the presentinvention, when using an oxide material as a main component, ischaracterized by excellent resistance to use environment and less loadto environment.

This application claims priority from Japanese Patent Application No.2004-254837 filed on Sep. 1, 2004, which is hereby incorporated byreference herein.

1. A method of producing an light-emitting device, comprising stepsof: 1) forming a first part having a first dielectric constant; and 2)forming on the first part a thin film layer that includes a second parthaving a second dielectric constant and a third part having a thirddielectric constant, so as to form a triple junction with a geometry ofa closed line, wherein the first part, the second part, and the thirdpart are in contact with each other.
 2. A method of producing alight-emitting device, comprising steps of: a) forming a member having,on a surface thereof, a first part having a first dielectric constantand a second part having a second dielectric constant; and b) forming onthe member a third part having a third dielectric constant, so as toform a triple junction with a geometry of a closed line, wherein thefirst part, the second part, and the third part are in contact with eachother.
 3. The method according to claim 1, wherein a region of thesecond part and a region of the third part are present in a film planeof the thin film layer.
 4. The method according to claim 2, wherein aregion of the first part and a region of the second part are present ina film plane of the member.